Stabilized motor fuel



Uni S a e Paten 2,933,379 i STABILIZED MOTOR FUEL Ellis 5%. Fields, cmc g 'm, and Allen Brehm, Grif- 'fith, Ind.,--assignors'to-Standard OilCo'mpany, Chicago,

111., a corporation of lhdiana v f No Drawing. Application January-16, 1958 i Serial N0. 709,195

1 Claims. 01. 44- -63) The present invention relates to new and useful com positions of matter, and particularly to stabilized light hydrocarbon distillate-fuels and to the method of stabilizing such materials against oxidative deterioration in the presence of metals or metal compounds which catalyze such oxidation, for example c pper; vanadium, manganese, cobalt, chromiumand the like, and compounds thereof. More particularly, the invention is directed to stabilized hydrocarbon motor fuels and to the method of stabilizing petroleum products.

Petroleum products, for example motor fuels, naphthas, Diesel fuels, fuel oils, etc. are susceptible to oxidative deterioration, particularly in the presence of metals 7 which are oxidation catalysts, for example copper, va-

nadium, cobalt, chromium, etc. and compounds thereof.

An example of such oxidative deterioration is the for-- mation of'gum and/or color infstorage or in use of certain types of motor fuels, particularly those obtained from cracking processes. In order to inhibit such gum and/ or color formation, it has been common practice to oxidants is also encountered in fuels which have been subjected to the copper chloride sweetening process.

It is an object of the present invention to provide light hydrocarbon distillate fuels resistant to oxidative deterioration. Another object of the invention is to provide a methodof inhibiting the oxidative deterioration of light hydrocarbon distillate fuels in the presence of metals or metal compounds which are oxidation catalysts. Still another object of the invention is to provide hydrocarbon motor fuels which are resistant to oxidative deterioration. A further object of the invention is to provide a-method ofinhibiting the oxidative deterioration of gasoline conteining; or coming in' contact with; metalsior metal com,- pbunds, -which catalyze such oxidative deterioration. Other objects and advantages of the invention will become apparent from the following description'thereof.

We have discovered that the foregoing objects canbe attained by incorporating in light hydrocarbon distillate fuels, normally susceptible to oxidative deterioration, a small but inhibiting amount, for example, from about 0.0001% to about 1.0%, preferably from about 0.003%

2,933,379 Patented Apr. 19, 1960 to about 0.05% of an 8-hydroxy quinoline derivative having the general structure in which a is a tertiary alkyl radical bsrr m about 41 about'24 carbon atoms.

.. Compounds of the above structure are readily prepared by heating to a temperature of from about 100 F. j to about 220? F., an equal molar mixture of S-hydroxy; Heating, with" stirring, is continued at about 220 F.while blowing the nitrogen'for about one hour or until there is no longer the odor of the azomethine.

quinoline and a tertiary alkyl azomethine.

Tertiary alkyl azomethinesuch as t-butyl-, t-amyl-, t-hexyl-, t-octyl-, t-nonyl, t-dodecyl-,

- t-octadecyh, and t-eicosyl-azomethines may be employed.

The preparation of the additive of the present.inven- 7 tion is illustrated by the following example:

EXAMPLE I I A mixture of 28.2 g. t-octyl azomethine (0.2 mole) and 29' 'g. (0.2 mole) S-hydroxy quinoline was heated and stirred. At 140 F. all solid has dissolved and reacted.

Heating was continued at 220 F. for 1 hour with N blowing. All the odor of the azomethine had disappeared. The product, .57 g.,

by the ASTM D-525 Induction Period Test is demonstrated by the data in Table I.

Table l Sampl Induction No. Composition Period,

Mins.

Gasoline No. 1--- 390 A+30g8b$rioduct of Example I per 1,000 hbls. 435 A+i p.p.i n: Copper (Acetate) 145 c-(lalolaggoduct of Example I per 1,000 bbls. 255 Gasbline 1%. 2+1 p.p.m. Copper (Acetate) roduet of Example I per 1,000 bbls. 130 E+ lbs. r oduet of Example I per 1,000 bbls. 240

The additives of the present invention are effective in reducing lead deposition resulting from the degradation of tetraethyl lead in gasoline during long periods of storage; leaded gasoline can contain from about 0.5 to about 5.0 milliliters tetraethyl lead per gallon of fuel. This property is demonstrated by the data in Table II which were obtained by storing samples of a gasoline containing 2.5 cc. tetraethyl lead per gallon, with and without additives, for a period of eight months at trations.

The values of and were obtained by the following procedure: The total contents (500 1:11.) of the quart bottle was filtered through a tar d fine sintered glass crucible. The filtered gasoline was evaluated for so uble guin by the ASIM D=381 Method. These results are shown in Table II as milligrams ASTM D-38l gum per 100 milliliters. The quart bottle was washed with a mixture of methanol, acetone and chloroform and all of the solids removed. The washings were put through the filter c uc le containing the lns l bl p e ious y ll cte an he eflluent collected in a clean receiver. The efiduent contained gasoline insoluble organic sediment since this mixture of solvents is excellent for dissolving fuel insoluble orirlation products except for lead compounds.

Evaporation of the etiiuent under conditions of the ASTM D-BSI Method gave the milligrams of insoluble organic sediment per 500 milliliters of fuel. These data are shown in Table II. At this point, the tared sintered glass crucible contained only fuel insoluble lead compounds which were determined quantitatively by drying and weighing the crucible. The results are shown iable II as milligrams, of insoluble lead per 500 milliliters. The column headed Milligrams total insolubles and soluble gum per 100. milliliters" represent the sum of the other three columns con: verted to a 100 ml. basis where necessary.

Additive A is N-N'-di-sec.butyl-p-phenylenc diamlne marketed as Du Pout Antioxidant No. 22.

The above data demonstrate that the combination of one pound per 1000 barrels gasoline of each of the antioxidant and thc additive of the present invention (No. 5) is more eficctive in inhibiting the degradation of tetraethyl lead and the oxidative deterioration of the hydrocarbon motor fuel than 25 pounds of the antioxidant per 1000 barrels of fuel (No. 2 and 4) or 5 pounds of the product of Example I per 1000 barrels of fuel (No. 3).

As noted above, the additives of the present invention are added to light petroleum distillates in small concen- However, they can also be handled in the form of concentrates in hydrocarbon distillatcs; which can be blended back in the finished composition to the desired concentration. The light petroleum distillates are conventionally produced by crude oil'fractionation, cracking processes, and special conversion processes such as reforming, alkylation,polymerization, etc. The light distillates have a boiling point of from about 90 F. to about 200 F.; those in the, gasoline. range boiling from; about 100 F. to about 400 F., and those in the diesel fuel and heating oils boiling in the range of from about 350 F. to about 700 F.

Percentages given herein and in the appended claims are by weight unless otherwise stated.

The additive of the present invention can be used in combination with antioxidants, anti-wear agents, agents to inhibit spark-plug fouling, corrosion inhibitors, etc.

While the. invention has. been described. and illustrated by way of preferred embodiments thereof, it will be apparent to those, skilled, in the art that variations and modifications may be made without departing from the scope of the, present invention as defined by the appended claims.

We claim:

1. A stabilized hydrocarbon light distillate oomposiio compri ing a major proportion of a. ght notrol nm dis illaio. no mal y susceptible to. oxidative deteriorati n aoaasro and a small but. s flioieut amount to inhibit. such oxidativc deterioration, of an 8-hydroxy quinoline derivative having the general structure in which R is a tertiary alkyl radical having from about 4 to about 24 carbon atoms.

5. A gasoline stabilized against oxidative deterioration containing from about 0.000l% to about 0.05% of an I 8-hydroxyquinoline derivative having the general structure IIIv t- CsHn N- CH:

6,. A hydrocarbon fuel for spark-ignition internal combustion engines comprising a major proportion of a pctroleum distillate in the gasoline distillation range, normally susceptible. to oxidative deterioration, from about 0.5 to 5.0 milliliters tetraethyl, lead per gallon of said distillate, which tetracthyl lead is susceptible to degradatlon and from about 0.0001% to about 0.05% of an 8- hydroxyquinoline derivative having the general structure in which R. is a tertiary alkyl radical of from about 4 to about 24 carbon atoms, whereby said oxidative deterioration of said petroleum distillate and said degradation of the tctraethyl, lead is inhibited.

-7. 'A hydrocarbon fuel as described in claim 6 in which R is a tertiary octyl radical.

References Cited in the file of this patent STATES PATENTS 2,030,033 McConnell Feb. 4, 1936v 2.136.788 Fairlec Nov. 15, 193.8, 2,128,961 Dietrich V.,..-, Apr. 30, 1940 2,372,588 Larsen Mar. 27, 1945. 2,647,824 Jones Aug. 4, 1953 2,861,975

Thompson .7 Nov. 25, 1958 

1. A STABILIZED HYDROCARBON LIGHT DISTILLATE COMPOSITION COMPRISING A MAJOR PROPORTION OF A LIGHT PETROLEUM DISTILLATE, NORMALLY SUSCEPTIBLE TO OXIDATIVE DETERIORATION AND A SMALL BUT SUFFICIENT AMOUNT TO INHIBIT SUCH OXIDATIVE DETERIORATION, OF AN 8-HYDROXY QUINOLINE DERIVATIVE HAVING THE GENERAL STRUCTURE 